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1 Flexibility mechanism
Degree of rotation about bond conformation
polymerization
Monomer various long chains (molecules of polymers)
Configuration Flexibility
collection of these long chains States and properties of Polymers 1. Ethane (CH3-CH3)
In different conformations (plastics, rubbers or fibers)
There are many possible conformations for
ethane, However, Interaction between H eclipsed
polymer chains can be flexible or rigid (stiff, non flexible) and polymers
produces the energy maximum and minimum.
could be crystalline or amorphous. Molecules take the conformation with lowest
energy.
staggered
Conformation: 3D spatial arrangement of atoms or groups that is The symmetry of the molecule gives 3
equivalent minima and maxima per revolution
changed under the effect of thermal motion, but doesnt involve
breaking of chemical bonds.
1 The energy barrier (eclipsed) is equal to 11.8 kJ mol-1. 2
2. n-butane (CH3-CH2-CH2-CH3)
?
2.10.4
If whole chain in trans, the chain has the largest end-to-end distance
consider an Alkane with n C, n-1 bonds, two end bonds don not contribute
to different conformation. Others are in one of 3 conformations (T, G, G). Rmax = nl cos
the number of conformations is 3n-3 . Due to symmetry and low possibility of 2
high energy states, the number of conformations less than 3n-3
1
Gauche states of torsion angles lead to flexibility 2.2 Conformation of an ideal chain
in the chain conformation
ideal chains (no long range interaction between repeat units)
polymer molecules prefer strongly one conformational state to other states, which solvent (surroundings)
Real chains interact with
are stiff
polymers have similar preferences for a number of different torsional states, themselves
which are flexible.
2
2. Freely rotating chain
Experimental and theoretical estimates of the
characteristic ratio (C) for polyethylene at 140C. Assumptions: all bond length (l) and bond angles () are fixed
ignores the variations of potential U(i)
all torsion angles are equally likely and independent of each other.
n n
R 2 = Rn Rn = ri rj
i =1 j =1
13 14
N- b mb N+ b
17